Azo dyestuffs



Patented Nov. 11 1952 AZO. DYESTUFFS Willy Mueller and Max schmidiRi h n Switzerand s nq s t Qi mite i'BasslaSw m? and a s s-firm.

Nmll aw n vAp ica Feb uary 1 9.50 S e ia NQ- 1 08- taeflan lhhmaw 25;,

9 Claims.

t i -k own that m y vatye tu s. be converted into so-called leuco' ester salts. The representatives of this group preferably employed in practice contain per dyestuff molecule 2 or more groupings of the formula OSO3--Me wherein Me indicates for example ammonium, sodium or another alkali metal. These leuco ester salts are a a l water-so ub e n a count of. the pre e ce of. he O Me g oup an ar ry table in neutra to alkaline med um, They canbe empl yed a c d t pec a y i s nd printing proce s worke Q1112 9 t is group of d es s nd in wh ch fi a h val; dyestufi on. which they a e'ba d; is. regener ted njthe fiber.

few dyestuffs have also already been prepared i h c n a 'eu othra uimne sulfuricjacid ester radical and also an azo group attached directly to an anthraquinone radical.

In the case of the dyestuffs ofthis type however the anthraquinone component was employed as diazo component and the selection of the diazotization components which are concerned is naturally limited.

' The present invention is basedon the observation that valuable new a zo dyestufis' are obtained whe c upl n so nqn n an ary of s keto carboxylic acid is employed which con- .tainslin the m ecu e th t grouping Of a leuco-sulfuric acid ester of the anthraquinone series and in which a bond exists between the amide nitrogen atom and an anthraquinone carbon atom in pl-position.

By the expression a bond between the amide nitrogen atom and an anthraquinone carbon atom in p-position" is to be understood for example a direct bond or a bond by way of a bridge member attached in ,B-position (see below).

The coupling components to be employed according: to the present, process can be produced by reacting 'a leuco ester of an anthraquinone compound which contains at least one amino group attached directly or through a bridge me ber w th a th qu non s a m in d osi ion, with su h: r qiflat ne a en as is capabl f i tr ducin t radicalof a 43- carboxylicracid. Asis, known the anthraquinone leuco esters generallyexist in the form of their allzali salts. They are not very stable in strong ediat par icul r y at e eva d p r tur uco estersalts of anthraquinoneswhich con a n at, least: ne am no gro p h re ar c n.- cerned for exa ple he u ste a t v o aminqanthraqu n ne hi h contain an am ne group attached directly to :a carbon atom in 2 s-sqsi io 0 t e. a hraquinq e n cleus hes exampl s m y e mentione he lan e est r; sal of z-amin a thraquinone, of, 3 -ha 'qgetn r for xample 3-bromoor especially 3-ch1 oro-2 -arnino= anthraquinone and also of 2:6:diaminoanth quincner Suc p o uc s can a sw be. emp a co t in t e min g ou i a radic l'., in: exam l a enz n a 1. l'..v attached tea ba bell tomuint t siti'on of t e anthraquinqnen dens by way of a direct c-q b n o by wa lqt a ridge' m m er-T As "bridge members a e. @91 mied. e mp e t as g up h ar gxylie acid mide grqun or vo the ereueines:

(3113, (EH) -S0'z-, -NHOO*NH-, -SOz-N and -N'-SO1-- As examples may be mentioned the leuco ester salts of 3-chloros2e(p-aminobenzoyl)T-amin anthraquinpne, of ln-(peaminobenzoyl)-a;ninoan; thr ui ne, an a s p oducts the. general o mu in which X and Y indicate hydrogen; allgyl, allroxy orhalogen as for example;

nd tnesrqdustct th isrmulla The eaetio can s itable be carried ut as 3 aqueous medium, if desired with addition of catalysts. In the case of the application of diketene the reaction in general proceeds easily even at room temperature or at the most slightly elevated temperature.

The acetoacetic arylides thus obtainable may be converted by reaction with acid halides (other than acetic acid halides) as for example acid halides containing at the most 13 carbon atoms, such as furane carboxylic acid halides. There may be used preferably aromatic acid halides of the benzene series such as diphenyl carboxylic acid halides, -p-chloro-benzoyl-chloride or especially benzoyl chloride. The so-obtained B -keto carboxylic acid arylides, for example the aroylacetic acid arylides are likewise suitable as coupling components. The coupling components of the present process are, on account of the presence of the leuco ester grouping, water soluble and, on account of the presence of the B-keto carboxylic acid grouping, capable of coupling. The diazo compounds with which the arylides of the B-keto carboxylic acids are coupled can for example contain sulfonic acid groups. Preferably however there are employed as diazo compounds such as are suitable for example for the manufacture of so-called ice-colors and contain no solubilizing group and especially no carboxylic acid or sulfonic acid group. As examples may be mentioned 2-nitro-4-methyl-l-aminobenzene, 4- chloro 2 nitro l aminobenzene, 5-chloro-2- methoxy-l-aminobenzene, 4-chloro-2-methyl-laminobenzene, 2-chloro-l-aminob'enzene, 2-nitro-l-aminob-enzene, 2-nitro-4-methoxy-1-amino benzene, 2-methy1-4-chloro-2-methoxy-1- aminobenzene and 2:S-dimethyl-l-aminobenzene.

Diazoazo compounds are also concerned as for example the diazo compound from 4-amino- 2:5:2'-trimethoxy-l l'-azobenzene. Diazo compounds containing sulfonic acid groups, as for example diazotized 1-amino-2-methoxybenzene- 5-sulfonic acid, are employed with advantage in those cases in which the application of diazo compounds without solubilizing groups leads to the formation of dyestuffs which in spite of the two sulfuric acid ester groups are not sufiiciently soluble. This is for example the case with diazo dyestuffs from the leuco sulfuric acid ester of 2&6 diacetoacetylamino anthraquinone; this compound contains two' keto methylene groups which are capable of coupling and it is preferable, in order to obtain sufliciently soluble products, to couple one molecule of this coupling component on one side with one mol of a diazo compound free from solubilizing groups and on the other side with one mol of a diazo compound containing sulfonic acid groups.

In the present process the coupling can be carried out inthe customary manner for example in a weakly alkaline aqueous medium containing sodium carbonate at temperatures between C. and about 2025"- C.

The dyestuffs obtainable according to the present process are new and correspond to the general formula in which R1 indicates the radical of a diazo component and R2 the radical of an arylide of a 5- keto carboxylic acid which is attached to the azo group by the carbon atom adjacent to the functionally converted carboxyl group of the s-keto carboxylic acid, which contains the atom grouping of a leuco sulfuric-acid ester of the anthraquinone series, and in which in addition a bond exists between the amide nitrogen atom and an anthraquinone carbon atom in fl-position.

The radical of the coupling components is set out below in the keto form but it is not to be understood that this indicates that the products concerned are incapable of also existing in the enol form.

These dyestuffs are suitable for the dyeing and printing of fibers of very varied nature, as for example animal fibers such as wool and silk and especially vegetable fibers such as cotton, artificial silk and also staple fiber from regenerated cellulose. The same dyeing and printing processes can be employed as are generally known for leuco ester salts and which depend in principle upon the fact that the soluble leuco ester salt is reconverted by simultaneous saponification and oxidation into the water-insoluble dyestuff which contains instead of a vatted radical the unvatted water-insoluble residue, for example an anthraquinone radical.

The following examples illustrate the invention, the parts and percentages being by weight:

Example 1 Into a solution of 51.3 parts of the disodium salt of the leuco sulfuric acid ester of Z-acetoacetylamino-anthraquinone and 25 parts of sodium carbonate in 250 parts of water there is allowed to flow at 5-8 C. within 10 minutes a diazo solution which has been obtained by diazotization of 18.75 parts of l-amino-4-ch1oro-2:5-dimethoxybenzene in 200 parts of water. The whole is stirred for 2 hours at 58 C. and then for 6 hours at 10-15 C. The dyestuff formed for the most part separates as a yellow crystallized precipitate. The Whole is now heated to 30-40 0., whereby the dyestuff passes into solution, treated with 40 parts of sodium chloride and stirred to complete separation of the dyestuff. Filtration is then carried out and the dyestuif Washed with 10 per cent sodium chloride solution and dried in vacuum at 50-60 C. The dyestuff is obtained in the form of a yellow powder which is easily soluble in water with a yellow color. Printed on cotton there are obtained after development with sodium nitrite and dilute sulfuric acid pure yellow shades of excellent wet fastness properties and fastness to chlorine and very good fastness to light.

The new dyestuff has the following constitution:

The disodium salt of the leuco sulfuric acid ester of 2-acetoacetylaminoanthraquinone can be produced in the following manner:

30 parts of chlorsulfonic acid are added drop by drop with good cooling and stirring to parts of pure dry pyridine and into the mixture obtained 26.5 parts of 2-acetylaminoanthraquinone and 12 parts of iron powder introduced. The mixture is heated during 4-6 hours to 50 C. and then poured into a solution of 50 parts of sodium carbonate in 1000 parts of water. The pyridine is removed by distillation under-reduced the remaining solution filtredffrelii iron sludge. From the filtrate on addition M 150 parts of sodium chloride is precipitated the disodium salt of the leuco sulfuric acid ester of 2-acetylaminoanthraquinone as a pale yellow crystal paste. The product is filtered with suction and washed with 20 per cent. sodium chloride solution.

The filter cake thus obtained is stirred with 50 parts of water and heated for 15 minutes to 80-90" C. with 50 parts of 30 per cent. caustic soda solution. After a short time the disodium salt of the leuco sulfuric acid ester of 2-aminoanthraquinone precipitates as a thick yellow crystal paste. This is allowed to cool and then diluted with an equal volume of alcohol, filtered and the-residue washed with-alcohol untilno 4 ifiiithei" excessjaugan be detected the filtrate. I'he disodium salt dissolves very easily in water with a strong yellow'grnfluorescerice.

42.9 parts of the disodium salt of the leuco sulfuric acid ester of z-aminoanthraquinone are dissolved in 150 parts of water and the solution if necessary neutralized with a few drops of 10 per cent. acetic acid. To this solution area'dded drop by drop at 510 0., 8.5 parts of diketene and the whole is stirred for about "10 hours at 5' l0" C. After this time the-disodium salt of the l co'su 1c acides'ter of "2"acetoacetylaininoanthrauumone has separated in crystalline form *a'ntl is filte're'd' off and if desired dried.

Example 2 s into solution, 40 parts 6: 'sodiumchlori'de n se the carried out until separation of the dyestuff i edium chloride 'solutionan'd dried vacuum at 50'-60'} C-. The dyestuff'is obtained oliible inwater with a y'ello'w color. Printed -bli cotton there are obtained after development with sodium nitrite and dilute sulfuric acid pure sewer-r111 yellow shades of very goodfastness to "ch 'ine ah'l liglit very good vvt f'ast'rless rtie s.

new-avenue e'onsponas to the formula 0-SOaNa A valuable dyestuff can be prepared in the above manner if the disodiumsalt of the leuco sulfuric acid ester of 3-chloro-2acetoacetylntrbducedar-ld stirring at room temperature 1 the-fennel a yellow powder which is easily i "is 6 am ifio'a'h'thraquinohe is replaced by the "disodium salt of the leuco sulfuric acid ester of s-brbrne- 2-acetoacetylaminoanthraquinone.

The disodium salt of the leuco sulfuric acid ester of 3 chloro 2 acetoacetylami noanthraquinone is obtained by condensation of the leuco sulfuric acid ester of 3-chloro-2-aminoanthra=- qluinone with 'c'iiketen'e in neutral aqueous solut on.

If there areemployed in the above example, "instead of the l=amino-4-chloro-2:5-dimethoxybenzene, 1255 parts of 1-amino-2-methoxybenzene, a dyestuff is obtained which in cotton printing after development with acid oxidizing agents gives somewhat more greenish pure yellow shades of equally .good fastness properties.

Example .3

.1027 :parts of 1-amino=4-"methylbenzene are .d-iazotized in the custcmar-y 'manner "a'nd the'diazo "solution allowed to flow at 5 8 "C. into a solution of 54.7:parts'of"th'e disodium saltof the leuco sulfuric acid ester "of .3-'chloro=-2=ac'etoacetyl- 'aminoanthraquino'ne and 301parts' of sodiumcarbonate in 250 parts of water. The whole is stirred for 2 hours ate-10 C. and 6 hours at 10-l5 C. Heating'is then effected to 40-45" C., parts of sodium chloride added and stirring carried "out "at room -ternperature to complete "separatidn 6f the l dyestuif. is -filtered with suction, washed with dilute'so'dium'chloridesolution and dried in vacuum at 50-60 C. A yellow powder is obtained which is easily soluble in water and which when printed on cotton and developed "with acid oxidizing agents gives pure powerful yellow shades of very good fastness properties.

By replacing in this example the 1-ammo 4- methylbenzene by an equivalent quantity of 1-amino-2 4-dimethoxy-5-chlorobenzene, there is obtained a dyestufi which when printed on cotton-and developedwith acid oxidizing agents .yieldspowerful gold 'orange shades of very =gocd i fast-ness 1 properties.

. Erizmple 4 lntb a solution-of 61.21parts of the disodium -salt'oftheleuco sulfuric acid ester of 2 6=dia cetoacetyl=aminoanthraduinone and '50 parts-'of'sodium' 'carbonate in 500 parts of water, there'isallowed to fio'w with'stirrin'g at -5--8"C."'a dia'zo solu- -tionipr'o'duced inknown manner-from 12.3.pa'rt's of -l alnino 2=rnethoxyb'erizene. The whole is stirred for 2 hours at 5 8" C. whereby the rdiazo -compound completely disappears. Thenionoazo'fdyestuff separate's for the most part in this 'opera- "tion. Then with further cooling to 5 8 20.; a dia'z'o s'oluti'on from 103 parts :of l'-amin'o=2- methoxybenzene 5=sulfonic acid in 200 p'arts'lof water is allowed'tofiowin. The diazo compound disappears rapidly with solutionof thje "mono'azo 'eyesmrraha with formation of a thick j'elly "mass. The wholefissti'rred for- 1 2 hours at room temperature and then slowly heated to 150 'whrebyacle r's'olution is obtained. l'oliparts of -sodi'u-m chloride are introduced and "stirring carried out at roorntefiiperature toc'ompleteseparatioh of the dyestufi. Thi S iS filtered with suction; washed with dilute sodium chloride soincensed the dyestufi obtained dried invac'uum at 50-60" C. There is obtained a yellow brown 'dy'estuff powderwhi'ch dissolves in water'with an orange color and when 'printedbn "cotton gives fatter jdveloplnehtwith aeid oizidizing egents yelnew shades; 1

The dyestuff corresponds to the following foroxidizing agents gives pure greenish-yellow mula shades.

O OCH3 C-CHi \CHN i) ll 0 H soin NHC\ HON=N O-BOsNa Hie-o HaC-O The disodium salt of the leuco sulfuric acid ester Example 6 of 2:6-diacetoacetylaminoanthraquinone is ob- 575 parts of the disodium salt of the leuco tained by esterification of 2:6-diacetylaminoan- Sulfuric acid ester of thraquinone in a mixture of pyridine and chlorbenzoyl) aminoanthmquinone of the formula sulfonic acid with the addition of iron powder, 0 so N w saponification of the diacetyl derivatives in 10 3 a T per cent. potassium hydroxide solution and con- C 0 CL; densation of the leuco sulfuric acid ester of 2:6- diaminoanthraquinone with diketene in neutral aqueous solution.

Example 5 $401M (obtained by condensation of the leuco sulfuric 543 parts of t disodium lt of t leuco 1- acid ester of Z-aminoanthraquinone with 3-nitrofuric acid ester of 2-(4'-amihobenzoy1amino)- 3o 4-methoxybenzoyl hl i e d r d i n f h anthraquinone of t formula, nitro group with sodium sulfide), are dissolved in 800 parts of water and at 58 C. with good stir- 0 SO3Na ring 8.4 parts of diketene added drop by drop. The whole is stirred for 12 hours at 5-10 C. O whereby the condensation product for the most part separates in the form of yellow crystals. 100

parts of potassium chloride are added, stirring is continued for a further 30 minutes and the prod- (IFSOQNa not is filtered and washed with dilute potassium chloride solution.

The quantity of the moist condensation product corresponding to 33.1 parts of dry substance benzoyl chloride and reduction of the nitro group 15 dlssiolved m 500 parts of Waiter Wlth 15 parts with sodium sulfide) are dissolved in 500 parts of of it q Solutlon 9 to 5 water and to this solution at 5-10 C., 8.4 parts of and to .wmhm t t dlazo Solutlon diketene added drop by drop. The whole is stirred added ontameil by dlazptlzatlon of pairts of at 5-10 C. until no more free amine can be de- P Y benzene m 200 tected in the solution and the condensation prodparts Water The whole 15 surfed for 2 hours uct is precipitated by addition of 80 parts of at 5-10 and 6 hours at 1045 The dyepotassium chloride. It is filtered with suction and stuff thergby separates (.zomplejcely is filtefred washed with dilute potassium chloride solution. wlth Suction Washed Wlth httle (mute sodmm The quantity of the moist condensation prodchloride sotution i dried Vacuum at 60-700 uct corresponding to 31.6 parts of dry substance Thgre g g m fifl manner yellowis dissolved in 500 parts of water with 15 parts of t yes u pow er W h dissolves Water sodium carbonate, the solution cooled at 0 C. with an orange color and whlqh t t p and into it allowed to flow within 30 minutes a M011 i devempment Wlth acld X1dizmg diazo solution obtained by diazotization of 9.4 agents glves pure gold'orange Shades of good (obtained by condensation of the leuco sulfuric acid ester of Z-aminoanthraquinone with p-nitroparts of 1-amino-4-chloro-2:5-dimethoxybenfastness P Q zene in 150 parts of water. The whole is stirred By replacing m h above p e the for 2 hours at Mr 0. and 6-8 hours at 1045 c. ch19m-1-ammO-2i5-dlmethoxy e e by 1- The dyestufi formed separates almost completely. benzene a dyestufi S Obtalned 50 parts of sodium chloride are added and Ship which when printed on cotton after development ring efiected to complete separation of the dye- Wlth acld oxldlzmg agents Elves p reddishstufi which is filtered and washed with dilute soyellow shadesdium chloride solution. After drying in vacuum p e 7 at 60'70 C., the dyestuff is obtained as a red- 57.8 parts of the disodium salt of the leuco brown powder which dissolves in water with an sulfuric acid ester of the anthraquinone conorange color and when printed on cotton after densation product of the following constitution development with acid oxidizing agents gives redousofiqa O CH3 dish-yellow shades of good fastness to boiling and chlorine. G C By replacing in this example the 4r-chloro-lamino-2:5-dimethoxybenzene by 2 nitro-4- methylaniline, a dyestufi is obtained which when printed on cotton after development with acid 40am,

(obtained by condensation of anthraquinone-3- carboxylic acid chloride with 1-formy1amino.-2- methoxy-4amino.-benzene, esterification of the,

condensation product obtained with chlorosulfonic acid in pyridine with the addition of iron:

and saponification of the for-myl amino group with per cent caustic potash solution) are dissolved in 500 parts of water and with stirring at 5-8 C., 8.4 parts of diketene added drop by drop. The whole is stirredfor 12 hours at 5.-10 C. Then the solution is treated with 25 parts of sodium carbonate and with cooling to 5 C., a diazo solution obtained by diazotization of 18.7 parts of 4-chloro 1 amino-2.:5-dimethoxybenzene allowed to flow in. The dyestuff formed separates after a short time as a thick yellow-brown precipitate. Stirring is carried out for 8 hours at 8-10 C. and the product is filtered and washed with. dilute sodium chloride solution. After dryingin vacuum at 50-60" C., the dyestuif' is obtained as a brown powder which easily dissolves in. water with an orange color. on cotton there are obtained; after development withacid' oxidizing agents yellow-orange shades of'eoo'difastness properties.-

Example 8 46.35 parts of the disodium' salt of the leuco sulfuric acid ester of 3-chloro-2-aminoanthraquinone are dissolved in 200 parts of water, 6.8 parts of sodium nitrite dissolved in 20 parts of water added and the mixture treated with 100 parts of crushed ice. With good stirring there are quickly added 30 parts of hydrochloric acid of 30 per cent strength, diluted with an equal volume of water. The whole is stirred for minutesand care is taken by the addition of'ice that the temperature does not exceed 3 C. To

the red suspension of the diazo compound obtainedthere is now added with stirring and cool.- ing a solution of 14 parts of 5-methyl-2-methoxy l-aminobenzene in 600 parts of alcohol. Within 3 hours a solution of parts of crystallized sodium acetate in 100 parts of water is added drop by drop and the whole then stirred for a further 12 hours at 10-l5 C. The monoazod'yestuff precipitated as a red precipitate is now filtered with suction and washed with dilute sodium chloride solution. The filter cake is then suspended in 300 parts of.water and treated with sodium carbonate to a neutral reaction whereby the wholepasses intosolution with a red-orange color. The solution is then cooled to 58 Ciand within one hour 8.4 parts of diketene introduced drop bydrop and thewhole stirred for a further 6 hours at 5'10C. In this operationithe color of the solution, turns. to yellow-orange. After the. odor of diketene has disappeared parts of sodium carbonate. and sufiicient ice are added so that. the temperature falls to 3 C. Then within. minutes a diazo solution is allowed to fiow in, obtained by diazotization of 15.75 parts of 5-chloro-2-meth0xy 1 aminobenzene in 200 parts of water. The whole is stirred for 2 hours at 0-5 G. and 12 hours at.10-15 C. and the precipitatedidyestufi filtered with suction. After drying in vacuum at 4.0-50. 0., there is obtained a dark powder which dissolves in water with a red color and when printed on cotton after development with acid oxidizing agents gives powerful. brown orange shades of good fasteness properti s.

The new dyestuif corresponds in constitution to thefromula When printed 0v 0 CH2 II O-GH:

, CH1 O-SOINI Example 9 28.7 parts of the amino. azo.

dyestuff of the formula.

are diazotized with 25 parts of 30 per cent. hydrochloric acid and 6.9 parts of sodium nitrite in 300 parts ofwater at 5-'7' C. The yellow-brown diazo solution is allowed to flow with stirring at 5-10" C. into a solution of 54.7 parts of the disodium salt'of the leuco sulfuric acid ester of 3- chloro 2 acetoacetylamino anthraquinone and 30 parts of sodium carbonate in 500 parts of water. The. whole is stirred for. 4'. hours at5-8, C.

and 12 hours. at. room temperature. Heating;

then carried out to 40-45; C.,.50-pa.rts of: sodium; chloride added. and thewhol'e. stirred untilflthe.

dyestuff has. completely separated. This is fil tered, washed with dilute, sodium chloride solue tion and dried in vacuum at: 50-60'C. The dyestufi is obtained in the form of adark powder: which dissolves in water with orange: color and when printed on. cotton. after: development with acid oxidizing agents yields. powerful red-orangeshades; of: oodfastness p perties;

The new dyestuff corresponds to the formula.

54.? parts of the disodium salt of the leuco sulfuric acid ester of 3-chloro-2-acetoacetylaminoanthraquinone are dissolved in 500 parts of waterwith 25 parts of sodium carbonate. Into the sodium, cooled to 5 C., is allowed to flow with good stirring within 30 minutes a diazo. solution from 14.3 parts of l-aminonaphthalene in 250 parts of water. The whole is stirred for 3 hours at 5-10" 0. and 6 hours. at 10'-15C. Heatingis then carried out to -50 C. whereby the dye.- stufi which has in part separated passes into solution, parts of sodium chloride stirred in and stirring continued at room temperature. until the precipitation of the dyestufi. is complete. This is filtered off, washed with dilute sodium chloride solution and dried in vacuum. at -'I0 C. The-dyestufi. is obtained in the form of an orange-colored powder whichis easily soluble in water with yellow-orange color and which when printed on cotton after development. with acid oxidizing agents gives; gold-yellow shades of very good fastness properties.

A dyestuif with similar properties is obtained when in the above example the l-amino-naphthalene is replaced by Z-aminonaphthalene.

Example 11 56.5 parts of the dipotassium salt of the leuco 4 are dissolved in 500 parts of water with 30 parts of sodium carbonate and to the solution cooled to -5 C. a diazo solution added with stirring, obtained by diazotization of 18.7 parts of 4- chloro-l-amino-2:5-dimethoxybenzene in 300 parts of water. The whole is stirred for 2 hours at 05 C. and hours at 8-12 C. The dyestuff for the most part separates. Heating is effected to 4550 C. until a clear solution is obtained, 50 parts of sodium chloride added and the whole stirred at room temperature until all the dyestuiT is precipitated. It is then filtered and washed with dilute sodium chloride solution. After drying in vacuum at 60-70 0., there is obtained a yellow brown powder which dissolves in water with a yellow color and when printed on cotton after development with acid oxidizing agents yields fast yellow shades. The new dyestuif corresponds to the formula The compound of the formula given employed as coupling component in the above example, can be prepared in the following manner:

54.4 parts of the dipotassium salt of Z-acetoacetylamino-3-chloroanthraquinone leuco sulfuric acid ester are dissolved in 400 parts of Water and 18.5 parts of per cent. sodium hydroxide solution added. At 05 C. with good stirring 17 parts of benzoyl chloride are added drop by drop within one hour. The solution becomes intensely yellow colored. Stirring at 0-5 C. is continued for a further 4 hours and then sufiicient acetic acid is added until blue litmus paper is just turned red whereupon A of the volume of 20 per cent. ammonia solution is added. The whole is heated to C. and the temperature maintained for one hour. Then the clear solution is evaporated in vacuum at 12 5060 C. until crystallization commences, allowed to cool and the product filtered and dried in vacuum at 60 C. The dipotassium salt of the 2 benzoylacetylamino 3 chloroanthraquinone leuco sulfuric acid ester obtained forms a white salt which is easily soluble in water.

Example 12 60.5 parts of the disodium 'salt of the leuco sulfuric acid ester of the following constitution ro-soiNa NH;

S OsNa (obtained by condensation of fi-aminoanthraquinone with 4-methoxy -3-'acetyl-aminoben zene-l-sulfochl-oride, methylation of the sulfonamide obtained, esterification of the condensation product with chlorosulfonic acid in pyridine in the presence of iron and saponification of the acetyl amino group with dilute potassium hydroxide solution) are dissolved in 300 parts of water. The solution is cooled to 5 C. and with stirring within one hour 8.40 parts of diketene added drop by drop. The whole is stirred at 5-10 C. until the odor of diketene has disappeared, 30 parts of sodium carbonate then added and with cooling to 58 C. within 30 minutes a diazo solution introduced obtained by diazotization of 18.7 parts of 4-chloro-l-amino-2:5 dimethoxybenzene in 306 parts of water. Stirring is effected for 2 hours at 5-8 C. and 12 hours at l015 C., then 40 parts of sodium chloride are added and the precipitated dyestuif filtered off. After drying in vacuum at 50-60 0., there is obtained a brown dyestuff powder which dissolves in water with an orange color and when printed on cotton after development with acid oxidizing agents gives gold-orange shades of good fastness properties.

Example 13 42.9 parts of the disodium salt of the leuco sulfuric acid ester of 2-aminoanthraquinone are dissolved in 250 parts of water and the solution if necessary neutralized with a few drops of dilute acetic acid. To this solution are added drop by drop at 15-20 C. with good stirring 8.5 parts of diketene and stirring effected for 2 hours at 20 C. The wholeis then treated with 25 parts of sodium carbonate and suificient ice to cause the temperature to fall to 0 C. and with stirring within 30 minutes a diazo solution allowed to flow in containing 16.8 parts of Z-nitro-l-methoxy aniline in the form of diazo compound. Stirring is carried out for 2 hours at 05 C. and 6 hours at 10-15 C., 20 parts of sodium chloride are added and the precipitated dyestuif filtered off. After drying in vacuum at 4050 C., a brown red powder is obtained which easily dissolves in Water with a red color. When printed on cotton and developed with sodium nitrite and dilute sulfuric acid pure orange shades are obtained of good fastness to boiling and chlorine.

Example 14 46.35 parts of the disodium salt of the leuco sulfuric acid ester of 3-chloro-2-aminoanthraquinone are dissolved in 200 parts of water, the solution exactly neutralized with dilute acetic acid and with stirring at 10-15 (3., 8.5 parts of brought into solution with a red color.

'13 diketene added drop by drop. In this operation the temperature rises to 18-20 C. Stirring is carried out at 20 C. for 2 hours after which time no more free aminoanthraquinone can be detected.. 25 parts of sodium carbonate are now added to the solution and sufiicient ice to cause the temperature tofallfto C. and within 30 minutes a diazo solution is allowed to flow in obtained by diazotization of 17.25 parts of 4-chloro-2-nitrani- 1ine-in200 parts of water. After a shorttime the dyestufi commences to deposit as an orange-red colored precipitate. Stirring is carried out for 2 hours at 0-5 C. and 6 hours at 10-15 C. Then 20 parts of sodium chloride are added for complete separation of the dyestuff, stirring is continued for one hour and the product isfiltered. After drying in vacuum at 40-50" C., a red-orange colored powder isobtained which is very easily soluble inwater with orange color. When printed on cotton there are obtained after development with sodium nitrite anddilute sulfuric acid pure yellow shades of outstanding 'fastness of boiling and chlorine.

Example 1 5 tization of 15.7 parts of 5-chloro-2-methoxy-aniline in 200 parts of water. Stirring is carried out for Zhours at 0-5 C. and 6 hours at 10-15 C. Then the solution is treated with 20 parts of sodium chloride, stirred until the dyestufi is completely separated and filtered. After drying in vacuum at 40-50 C., a red powder is obtained which iseasily soluble in water with red-orange color; When printed on cotton there are obtained'after development with sodium nitrite and dilute sulfuricacid pure reddishyellow shades of good fastness to boilingand chlorine.

Ealample 16' 46.35 parts of the disodium" salt' of the leuco sulfuricJacid ester of 3-chloro-2-aminoanthra quinone are. dissolved in200. parts of water,..6'.8 parts or sodium. nitrite. dissolved in 20. parts. of water; added. and the. mixture-:1 treated with 1 00 partsof crushed ice. are added inoneoperation 30 parts of concentrated hydrochloricacid. Stirring is carried out for minutes and care is taken by addition of ice that the-temperature does not exceed 0-3 C. Into the red suspension of the diazo compound obtained there is then allowed to flow with stirring and cooling a solution of 14 parts of 5-methyl-2-methoxy-1-aminobenzene in 100 parts of alcohol. Within 3 hours a solution of parts of crystallized sodium acetate in 100 parts of water is added drop by drop and stirring then continued for 12 hours at 10-15 C. The monoazo dyestuff separated as a red precipitate is then filtered with suction and Washed with dilute sodium chloride solution. The filter cake is then suspended in 7 300 parts of water, sodium carbonate added to a neutral reaction and in this manner the whole Then at 10-15 C., 8.4 parts of diketene are added drop by drop and stirring carried out for 3 hours at With good stirring: there 1 14 20 C; i In this'operation theJ-color'for thesolution changes from red to orange. After the odor. of diketene has disappeared, 25 parts of sodium carbonate are added and'sufiicient ice' to cause the temperature to fall to 0 C. Then within 30 minutes a diazo solution is allowed to flow in, obtained by diazotization of 17.25 parts of 4-chloro-Z-nitraniline in 200 parts of water. Stirring is carried out for 2 hours at 05 C. and 12 hours at 10-15" C. The dyestuff separates as a brown precipitate. After filtration with suction and drying in vacuum at 40-50 C., a dark powder is obtained'which dissolves in water with a red violet color and when printed on cotton after development with sodium nitrite and dilute sulfuric acid gives powerful red-brown shades of'good fastness properties.

Example 17 A printing paste is prepared. from:

parts of the: dyestufi obtained according to Example. 14, 50 parts of thiodiethylene glycol, 50 parts of stiffener, 220 parts of water, 550 parts of starch tragacanth thickening,

50 parts of 30 per cent. sodium nitrite solution, 20 parts of 10 percent sodium carbonate solution 1000 parts After printing .steaming is carried out for 5 minutes in the Mather-Flatt and subsequently development effected on the foulard' in a bath containing 20 parts of sulfuric acid of 95 per cent. strength in 1000 parts of waterat' C. for at least 10 seconds. After squeezing out the material has a passage through the air of 20-30 seconds and is then rinsed and then soaped for 10 minutes at the boil, rinsed again and dried. There are obtained in this manner powerful prints of pure greenish yellow shades.

What we claim is:

An azo dyestuff of the formula in which R1 stands for the radical of a diazo; component of? thebenzene series free from solubilizing groups, R5 stands for a radical of a leuco sulfuric acid ester of an anthraquinone attached in fi-position of the antraquinone nucleus directly to X, and X stands fora member selected. from the group consisting of a direct linking bond and in which radicals R7 stands for a benzene radical.

2. An azo dyestuif of the formula p in which R1 stands for the radical of a diazo component of the benzene series free from solubilizing groups and R5 stands for a radical of a leuco sul- 15 furic acid ester of an anthraquinone attached in fl-position of the anthraquinone nucleus directly to the -HN-- group.

3. An azo dyestuff of the formula :in which R1 stands for radical of a diazo component of the benzene series free from solubilizing groups and Rs stands for a leuco sulfuric acid 15 ester of the radical in which R1 stands for the radical of a diazo component of the benzene series free from solubilizing groups and Rs stands for a leuco sulfuric acid ester of the radical 5. A leuco sulfuric acid ester of the azo dyestuff of the formula 6. A leuco sulfuric acid ester of the azo dyestuff of the formula HBO-O O O-CH: CCH:

7. A leuco sulfuric acid ester of the azo dyestuff of the formula 8. A leuco sulfuric acid ester of the azo dyestuff of the formula O-GH:

O H n C-HN ll @1- 9. A leuco sulfuric acid ester of the azo dyestuff of the formula WILLY MUELLER. MAX SCHMID. REFERENCES CITED The following references are of record in the file of'this patent:

UNITED STATES PATENTS Number Number Name Date Mannes et a1 Feb. 15, 1938 Stallman May 17, 1938 a Vittum et al Aug. 4, 1942 Besler Apr. 18, 1944 FOREIGN PATENTS Country Date Great Britain Dec. 31, 1941 

9. A LEUCO SULFURIC ACID ESTER OF THE AZO DYESTUFF OF THE FORMULA 